Resilient material of particulate rubber in a binder of butadiene and coumaronl indene polymers

ABSTRACT

An article of manufacture and a process for producing same is provided. The article is comprised of discrete particulate matter bound into a solid resilient mass by a binder material comprised of a butadiene-styrene copolymer and a tackifying resin.

United States Patent [191 Bennett et a1.

[451 Apr. 10, 1973 RESILIENT MATERIAL OF INDENE POLYNIERS [75]Inventors: Richard J. Bennett; Duane W. Ga-

gle, both of Bartlesville, Okla.

[73] Assignee: Phillips Petroleum Company, Bartlesville, Okla.

[22] Filed: Mar. 10, 197i [2]] Appl. No.1 123,049

[52] U.S. Cl ..260/829, 260/2.3, 260/27 BB, 260/41.5 A, 260/4l.5 R,260/846, 260/887, 260/890 [51] Int. Cl. ..C08f 39/00 [58] Field ofSearch ..260/ 829 [56] References Cited UNITED STATES PATENTS 2/1971Nyberg ..260/876 Hall ..260/829 FOREIGN PATENTS OR APPLICATIONS 906,2259/1962 Great Britain" ..260/829 Russell ..260/ 829 Primary ExaminerPaulLieberman AttorneyYoung & Quigg ABS I'RACT An article of manufacture anda process for producing same is provided. The article is comprised ofdiscrete particulate matter bound into a solid resilient mass by abinder material comprised of a butadiene-styrene copolymer and atackifying resin.

9 Claims, No Drawings RESILIENT MATERIAL F PARTICULATE RUBBER IN ABINDER 0F BUTADIENE AND COUMARONL INDENE POLYMERS This invention relatesto a resilient article of manufacture comprised of particulate matter,such as rubber particles, and a binder material, such as a high greenstrength butadiene-styrene copolymer and to a process v for producingsame.

It is desirable to utilize waste materials or potential waste materialsand products in useful articles and processes. Such use of waste orsalvage materials, when possible, cuts off a source of pollution at itssource, and is accordingly of a beneficial economic nature, andpromotive of an improved environmental life style.

It is thus the object of this invention to provide a useful resilientarticle of manufacture and a process for producing same, whereby theprincipal ingredient of the article is particulate matter which wouldotherwise be a waste material.

Other objects, aspects, and the many advantages of this invention willbe apparent to one skilled in the art from a'study of followingspecification and appended claims.

In accordance with this invention, there is provided an article ofmanufacture comprised of discrete particulate matter in combination witha binder material comprised of a high green strength butadiene-styrenecopolymer and a resinous tackifier. The article is a dry solid materialhaving a spongy, matted appearance which is caused by the fact that thediscrete particulate matter is bound together by the binder material ina nonuniform, irregular pattern. The article has a rough texture; it isquite resilient and immediately reassumes its shape upon release ofapplied pressure.

The resilient article can be fonned in place as a covering for largeunbroken areas; it is useful as a resilient mortar; and it is useful asa premolded article. Thus the resilient material of this invention isuseful as a covering for floors and outdoor surfaces such as athletictracks and fields, horse-race tracks, playgrounds, and the like. Inaddition, the resilient material of this invention is useful inpremolded items such as athletic padding, upholstery and furniturepadding, shock or impact padding and paneling in vehicles, and similarapplications. Also, the material has use as an undercoating and sounddeadening agent, and as an antiskid surface for pavements and bridges aswell as for stair treads, ramps, and similar skid and slip hazard areas.The material also has use in abrasion resistance applications and as asealant, a caulking compound, a joint filler, and as a mortar in thoseapplications where a resilient bond is required.

The resilient material develops good strength without need forvulcanization or chemical curing. That is, upon completion of itsmanufacture, as hereinafter described, it is immediately available foruse without further treatment being required.

The weight ratio of particulate matter to binder material present in theresilient article of this invention is in the range of 100 parts byweight particulate matter per 6 to 60, preferably to 40, parts by weightbinder material wherein the weight ratio of copolymer to tackifier inthe binder material is in the range of 1:1 to 4:1, preferably 2:1 to3:1, parts by weight copolymer per part by weight tackifier. Thepresently preferred embodiment contains 33 parts by weight bindermaterial per 100 parts by weight particulate matter wherein the ratio ofcopolymer to tackifier is 2 to 1 such that the weight ratio ofparticulate matter to copolymer to tackifier is 100 to 22 to l l.

The particulate matter useful herein comprises a diverse selection ofwaste or salvage aggregate material such as tire buffings, i.e., thatmaterial removed, scraped, or abraded from vehicle tires duringbalancing, rubber chips, such as from old useless tires, vulcanizedrubber chips, synthetic resins, metal turnings, wire, gravel and smallrocks, glass, seed bulbs, wood chips, sawdust, vegetable fibers, sand,ceramics, and similar waste materials and mixtures thereof.

The high green strength butadiene-styrene copolymer, i.e., thecopolymer, constitutent of the binder material is one of a branchedblock copolymer and a linear block copolymer both as hereinafterdefined.

The branched block copolymer is comprised of conjugated dienes andmonovinyl substituted aromatic compounds and has at least threerelatively long block copolymer branches which radiate from a nucleus.The terminal polymer block segments on each of the branches are composedof the monovinyl-substituted aromatic compound. Therefore, the termbranched block copolymer as used herein is intended to mean copolymershaving the general formula wherein each D group is a terminal blocksegment comprising essentially vinyl aromatic units, each C group is aconnecting polymer block segment comprising essentially conjugated dieneunits, the Z group is derived from a polyfunctional compound having atleast three reactive sites, and n is not less than three.

The branched block copolymer, as herein defined, must have at leastthree block copolymer branches radiating from a nucleus. Each of theblock copolymers in each branch has at least two polymer block segmentsmade from conjugated dienes and vinyl aromatic compounds.

The relative amounts of the vinyl-substituted aromatic compound and theconjugated diene used in producing the branched block copolymersdescribed above can vary over a wide range. The amount of conjugateddiene present in the branched block copolymer can be present in therange from 40 to parts by weight per parts by weight of the branchedblock copolymer. The vinyl-substituted aromatic compound can be presentin the range of from 5-60 parts by weight per 100 parts by weight of thebranched block copolymer. Preferably, the conjugated diene will bepresent in an amount of from 50 to 90 parts by weight per 100 parts byweight of the branched block copolymer.

The amount of vinyl-substituted aromatic compound that is present asterminal polymer block segments in the branched block copolymers used inthis invention can vary over a wide range. It is desirable that theterminal polymer block segments comprise the vinyl-substituted aromaticcompound to the extent of at least 5 percent by weight of the branchedblock copolymer.

The vinyl-substituted aromatic compound can be polymerized for a periodof time to produce a polymer block segment of the vinyl-substitutedaromatic compound of sufficient size followed by a second polymerizationstep wherein the conjugated diene is polymerized. In some instances itmay be desirable to allow all of the vinyl-substituted aromatic compoundto be polymerized before adding the conjugated diene for the secondpolymerization step. In other instances, any unreacted vinyl-substitutedaromatic compound can be removed from the polymerization mixturefollowed by the addition of the conjugated diene for the secondpolymerization step. And in still other instances, any unreactedvinyl-substituted aromatic compound may be left in the polymerizationsystem and the conjugated diene can be added for the secondpolymerization step. In the latter instance, the polymer block segmentsformed in the secondpolymerization step may contain both conjugateddiene monomer units and vinyl-substituted aromatic monomer units.

It is preferable that the terminal polymer block segments on thebranched block copolymer be homopolymer blocks of the vinyl-substitutedaromatic compound. However, it is also within the scope of thisinvention to utilize branched block copolymers with terminal polymerblock segments that are predominantly vinyl-substituted aromaticpolymers with minor amounts of the conjugated diene monomer units. Whenthe terminal polymer blocks are composed of both vinyl-substitutedaromatic units and conjugated diene units, the conjugated dienecomprises less than parts by weight for each 100 parts by weight of theterminal polymer block, with the vinyl-substituted aromatic comprisingthe remainder.

The vinyl-substituted aromatic compounds that can be used in producingbranched block copolymers for use in the adhesive composition of thisinvention can have up to about 24 carbon atoms per molecule and include:styrene, l-vinylnaphthalene, 2-vinylnaphthalene and the alkyl,cycloalkyl, aryl, alkaryl, and aralkyl derivatives thereof. Examples ofsuch substituted monomers include: a-methylstyrene, 3-methylstyrene,4-n-propylstyrene, 4-cyclohexylstyrene, 3-phenylstyrene,4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- p-tolyl-styrene,4-(4-phenyl-n-butyl)styrene, 3,6-di-nhexyl-l-vinylnaphthalene, and thelike.

The conjugated dienes used in the production of branched blockcopolymers for incorporation in the adhesive recipes of this inventionare those which contain from four to 12 carbon atoms per molecule. Theconjugated dienes containing from four to eight carbon atoms arepreferred. Examples of such compounds include 1,3-butadiene, isoprene,2,3-dimethyl-l,3-butadiene, piperylene, 1,3-octadiene,3-butyl1,3-octadiene, l-phenyl-l ,B-butadiene and the like.

The above referred to Z group which forms the nucleus from which thepolymer blocks of the branched block copolymer radiate is derived from apolyfunctional compound having at least three reactive sites capable ofreacting with a carbon-lithium bond. Types of polyfunctional compoundswhich can be used include the polyepoxides, polyisocyanates, polyimines,polyaldehydes, polyketones, polyanhydrides, polyesters, polyhalides andthe like. As will be hereafter described, the polymer block segments arepolymerized in the presence of an organomonolithium initiator. It ispreferred that the amount of polyfunctional compound utilized be 1.0equivalent per equivalent of carbon-lithium in the polymer for maximumbranching. Reference to U. S. Pat. No. 3,281,383 will reveal furtherdetails of the polyfunctional compound useful in the formation of thebranch block copolymers.

The branched block copolymers can be formed by any method known in theart, such as the method set out in U. S. Pat. No. 3,281,383. Briefly,this method of forming the branched block copolymers is as follows. Thevinyl-substituted aromatic compound is polymerized first in the presenceof an organomonolithium initiator. After the vinyl-substituted aromaticcompound has been polymerized to form the initial polymer block, theconjugated diene can be added to the polymerization mixture to produce ablock copolymer of the conjugated diene and the vinylsubstitutedaromatic compound. By the procedure of polymerizing thevinyl-substituted aromatic compound first, followed by the addition ofthe conjugated diene compound, a block copolymer having a terminallithium atom is formed. The lithium atom will be at the end of theconjugated diene polymer block. The lithium terminated block copolymeris called a living polymer because of the presence of the lithium atomat the end of the conjugated diene polymer block. The living polymer canthen be conveniently reacted with a polyfunctional compound having atleast three reactive sites that are capable of reacting with thecarbon-lithium bond of the living polymer. By regulating the amounts ofthe living polymer and the amounts of the polyfunctional compound, it ispossible to produce a branched block copolymer having at least threerelatively long polymer branches extending outwardly from the nucleus.The nucleus or hub is formed by the polyfunctional compound whichreacted with the lithium-terminated polymer. In order to produce thebranched block copolymers having at least three polymer branches, it isessential that the polyfunctional compound have at least three reactivesites that are capable of reacting with the carbon-lithium bond of theliving polymer.

To achieve maximum branching the optimum amount of polyfunctionalcompound that is reacted with the living polymer will be an amount ofpolyfunctional compound that contains one equivalent of treating agentfor each living polymer molecule. In other words, each reactive site onthe polyfunctional compound will react with a carbon-lithium bond in theliv-' ing polymer. Larger amounts of the polyfunctional compoundencourage the production of polymers that are coupled in a linearconfiguration instead of being branched. When equivalent amounts of thepolyfunctional compound and the living polymer are reacted, the finalproduct comprises a branched polymer in which the polymer chain' isjoined at one end to each reactive site of the treating agent.

Since the branched block copolymers used in this invention preferablycontain terminal homopolymer blocks of the vinyl-substituted aromaticcompound, it is necessary that the vinyl-substituted aromatic compoundbe polymerized first when an organomonolithium initiator is used to formthe block copolymer. After the vinyl-substituted aromatic compound hasbeen polymerized to the desired length, any unreacted vinylsubstitutedaromatic compound can be removed. The

conjugated diene is then added to the polymerization mixture and thepolymerization is continued until the conjugated diene has beenpolymerized to the desired amount. The living polymer of thevinylsubstituted aromatic compound and the conjugated diene thus formedcan then be reacted with the polyfunctional compound to produce thebranched block copolymer. In some instances, it may be desirable to formother polymer blocks before the living polymer is reacted with thepolyfunctional compound. This is very easily accomplished by simplyadding additional monomer increments to produce additional polymerblocks before the living polymer is reacted with the polyfunctionalcompound. Thus, it is possible to produce block copolymers having 2,3,or more separate and distinct polymer blocks by the above procedure.

The term linear. block copolymer is intended to mean copolymers havingthe general formula ABA wherein each A group is a block segmentcomprising a homopolymer of a vinyl-substituted aromatic hydrocarbon,and each B group is a block segment comprising a copolymer of aconjugated diene and a vinyl-substituted aromatic hydrocarbon.

The linear block copolymers of this invention contain three polymerblock segments made from conjugated dienes having four to about 12carbon atoms per molecule and vinyl-substituted aromatic hydrocarbonshaving no more than about 24 carbon atoms per molecule. The three blocksegments are joined together end to end such that there is a centralcopolymer block segment of the conjugated diene and the vinyl aromatichydrocarbon and two end or terminal essentially homopolymer blocksegments of the vinyl aromatic hydrocarbon. At least 45 weight percentof the total vinyl aromatic compound in the linear block copolymershould be in the terminal homopolymer blocks.

The preferred conjugated dienes which are used to prepare the linearblock copolymers of this invention include 1,3-butadiene, isoprene, andpiperylene. Other conjugated dienes which can be used include 2,3-dimethyl-l ,S-butadiene, 1,3-octadiene, 3-butyl-l ,3-octadiene,l-phenyl-l,3-butadiene, and the like. The vinyl-substituted aromatichydrocarbons which can be employed include styrene, l-vinylnaphthalene,2-vinylnaphthalene, and alkyl, cycloalkyl, aryl, alkaryl and aralkylderivatives thereof such as a-methylstyrene, 3- methylstyrene,4-n-propylstyrene, 4-cyclopentylstyrene, S-phenylstyrene,2-ethyl-4-benzylstyrene, 4-ptolylstyrene, and 3-dodecyll-vinylnaphthalene.

The linear block copolymers of this invention can be prepared by anymethod known in the art such as by the method described in U. S. Pat.No. 3,287,333.

The resinous tackifier which is useful in this invention can be any ofthe resinous substances known in the art for enhancing the tack ofadhesive compositions. Examples of some suitable tackifiers includerosin; dehydrogenated rosin, rosin plus polyterpene resins, e.g.,polymerized beta-pinene (from 100 percent rosin to 100 percent resin);hydrogenated rosin esters of glycerol; hydrogenated rosin esters ofpentaerythritol; coumarone-indene resins; hydrogenated rosin; esters ofpolymerized rosin and glycerol; maleic anhydridemodified rosin and rosinderivatives; partial esters of styrene-maleic acid copolymers;chlorinated biphenyls; oil-soluble phenol-aldehyde resins; and the like.

The surface of the particulate matter must be contacted with the bindermaterial in order to produce a satisfactorily bound product. In fact,the better the contact established between the entire surface of theparticulate matter and the binder material the better and more cohesivewill be the solid, resilient article of this invention. Best results areobtained when all the surfaces of the particulate matter are completelycontacted with the binder material. Accordingly, to establish thedesired contact the particulate matter can be contacted with a solutionor dispersion of the binder material. In one technique the loose,unbound particulate matter can first be placed in a mold or otherwisearranged in the shape, size, thickness, and configuration desired of thefinished solid article. The solution or dispersion of binder materialcan then be poured, sprayed, or otherwise applied to the preplacedarrangement of particulate matter. Upon evaporation of the solvent ordispersant the resilient article is complete and ready for use.

The quantity of solvent or dispersant utilized is sufficient toconveniently enable the complete contact of the entire surface of theparticulate matter with the desired quantity of binder material.Although the actual quantity of solvent or dispersant is not ofparticular critical importance, a convenient quantity is in the range ofabout 1 to 5 parts by weight solvent per one part by weight bindermaterial. In the preferred embodiment the weight ratio of solvent tobinder material is approximately 41 parts by weight solvent per 33 partsby weight binder material.

The solvents or dispersants useful herein reduce the viscosity of thebinder material and serve to wet the surface of the particulate matter.Although any organic solvent which is inert toward the other componentsof the mixture can be used, the preferred solvents are saturatedaliphatic, saturated cycloaliphatic, and aromatic hydrocarbons, e.g.,pentane, 2-methylpentane, hexane, 3-ethylhexane, heptane, octane,nonane, naphtha, cyclopentane, methylcyclopentane, cyclohexane,methylcyclohexane, benzene, toluene, xylene, and the like. Other liquidorganic solvents can be used, e.g., halogenated hydrocarbons such astrichloroethylene, ethers, ketones, esters, and the like. Mixtures ofthe above solvents are also useful, with the presently preferredembodiment having a solvent mixture consisting of trichloroethylene andxylene wherein the trichloroethylene is present to the extent of aboutpercent by weight of the solvent mixture.

Particularly satisfactory results can be obtained by applying the bindermaterial to the particulate matter in the form of an emulsion comprisingthe binder material, the solvent/dispersant, water, and a suitablequantity of a cationic surfactant wherein the quantity of water utilizedin the emulsion is in the range of 20 to percent by weight of theemulsion.

The emulsion can also contain other ingredients such as fillers,pigments, stabilizers, antiozonants and the like.

EXAMPLE In five experimental runs, five resilient articles were made asfollows: Tire buffings larger than No. Tyler sieve mesh were combinedwith an emulsion of the binder material in a suitably large container.The buffings and emulsion were thoroughly stirred until a uniformlythorough mixture was obtained. When the buffings-emulsion mixtures werethoroughly mixed, a portion of each mixture was transferred to aseparate circular metal form, each being about 6 inches in diameter andabout re-inch deep. Each mixture was compacted into its form with aroller and excess liquid was poured off. Each compacted mixture was thenallowed to stand for 24 hours at room temperature (approximately 75F.)during which time the fluid evaporated to thus produce theabove-referred-to five finished resilient articles of this invntion. Therecipe for each run is set out in Table I below:

resinous tackifier wherein the weight ratio of said particulate rubberto said binder material is in the range of 100 parts by weightparticulate rubber per 6 to 60 parts by weight binder material whereinthe weight ratio of said copolymer to said tackifier is in the range of1:1 to 4:1.

2. The article of claim 1 wherein said copolymer is one of a branchedblock copolymer and a linear block copolymer wherein: said branchedblock copolymer is comprised of at least three block copolymer branchesradiating from a nucleus, each of said block copolymer branches havingat least two polymer block segments made from conjugated dienes whichcomprise 40 to 95 percent by weight of said branched block copolymer andvinyl aromatic compounds which comprise 5 to 60 percent by weight ofsaid branched block copolymer; and wherein said linear block copolymeris comprised of a first block segment, a second block segment, and a"fIiiiJE' 1 MM Binder material Solvent Produced articles Tno Copoly-Trichloro- Surlec comparison ltun bullings mcr, Rosin, ethylene, Xylene,Water, tent. of particle number grams grams grams grams grains gramsgrains bonding 1 a. 100 6. (i 3. 3 7. 44 -l. .18 (i. 705 0. 795 5 g 10011 5. 5 12. 4 8. 3 11.175 1. 325 3 3 100 22 11 .24. 8 l6. 6 22. 2. 65 14 100 5. 5 .2. 75 G. 2 4.15 30. 5875 0. 6625 t 5 100 11 5. 5 12. 4 8. 361. 175 1. 325 2 None:

1. A commercially available branched block copolymer. 2. Acoumarone-indene resin. 3. A commercially available cationic surfactant.

Thea rti cl e produced in Run Texhibited the best par ticle bonding ofthe five articles made in the five runs. The article 3 was bonded to,and removable from, the metal form and had excellent bonding between andaround the particulate tire buffings. Article 5 was about the same asarticle 3 with respect to particle bonding, and article 2 was alsobonded to, but removable from,

third block segment wherein said second block segment, a copolymer of aconjugated diene having four to 12 carbon atoms per molecule and avinyl-substituted aromatic compound having no more than 24 carbon atomsper molecule, is sandwiched between said first and said third blocksegments both of which are homopolymer blocks of said vinyl-substitutedaromatic the metal form and had good particle bonding. In sumcompoundmation, the best particle bonding results were obtained with article 3with particle bonding results descending therefrom as follows;,articles5, 2, 4, and 1. Article 1 could be picked up as a cohesive unit, butthere was very little bonding between particles.

It is noted that the quantity of water utilized had a beneficial effectupon the quality of the particle bonding. Thus, whereas the bindermaterial and other emulsion ingredients were reduced by 50 percent as 3.The article of claim 2 wherein said copolymer is said branched blockcopolymer.

4. The resilient material of claim 1 wherein said particulate rubberconsists of tire buffings.

5. A process for the preparation of a resilient article comprised of acured particulate rubber and a binder material comprised of an uncuredhigh green strength butadiene-styrene copolymer and a coumarone-indeneresinous tackifier, said process comprising contacting between runs 3and 5 exceptthatthere was increase said particulate rubber with saidbinder material in a in water content of about 2.7 to l the producedarticles 3 and 5 were about the same with respect to particle bonding.Comparison of run 5 with run 2 and run 4 with run 1 similarly shows thatincreasing water content sufficient quantity of an organic solvent tothus form a mixture, forming said mixture into a configuration desiredof said article when complete, and permitting said solvent to evaporatefrom said formed mixture to of the emulsion produced better resilientarticles where thus produce the completed, dry, solid resilient articlethe other emulsion ingredients are or are about the same.

Reasonable variations and modifications of this invention can be made,or followed, in view of the foregoing disclosure, without departing fromthe spirit 50 or scope thereof.

Having described our invention that which is claimed is:

wherein the weight ratio of said particulate rubber to said bindermaterial is in the range of 100 parts by weight particulaterubber per 6to parts by weight binder material wherein the weight ratio of saidcopolymer to said tackifier is in the range of l:l to 4:1, and furtherwherein said copolymer is one of a branched block copolymer and a linearblock copolymer wherein: said branched block copolymer is 1. A resilientarticle of manufacture comprised of a comprised of at least three blockcopolymer branches cured particulate rubber in combination with a bindermaterial comprised of an uncured high green strength butadiene-styrenecopolymer and a coumarone-indene radiating from a nucleus, each of saidblock copolymer branches having at least two polymer block segments madefrom conjugated dienes which comprise 40 to percent by weight of saidbranched block copolymer and vinyl aromatic compounds which comprise to60 percent by weight of said branched block copolymer; and wherein saidlinear block copolymer is comprised of a first block segment, a secondblock segment, and a third block segment wherein said second blocksegment, a copolymer of a conjugated diene having four to 12 carbonatoms per molecule and a vinyl-substituted aromatic compound having nomore than 24 carbon atoms per molecule, is sandwiched between said firstand said third block segments both of which are homopolymer blocks ofsaid vinyl-substituted aromatic compound.

6. The process of claim 5 wherein the weight ratio of said solvent tosaid binder material is in the range of l to 5 parts by weight solventper one part by weight of said binder material.

7. The process of claim 6 wherein said binder material is contained inan emulsion, said emulsion being comprised of said binder material, saidorganic solvent, water and a suitable surfactant wherein said water insaid emulsion is present in the range of 20 to 65 percent by weight ofthe total weight of said emulsion, and during said evaporation step saidwater evaporates as well as said solvent.

8. The process of claim 7 wherein said solvent is a mixture oftrichloroethylene and xylene wherein said trlchloroethylene is presentin said solvent mixture to the extent of about 60 percent by weight ofthe total weight of said solvent mixture.

9. A process according to claim 5 wherein said particulate rubberconsists of tire buffings.

2. The article of claim 1 wherein said copolymer is one of a branchedblock copolymer and a linear block copolymer wherein: said branchedblock copolymer is comprised of at least three block copolymer branchesradiating from a nucleus, each of said block copolymer branches havingat least two polymer block segments made from conjugated dienes whichcomprise 40 to 95 percent by weight of said branched block copolymer andvinyl aromatic compounds which comprise 5 to 60 percent by weight ofsaid branched block copolymer; and wherein said linear block copolymeris comprised of a first block segment, a second block segment, and athird block segment wherein said second block segment, a copolymer of aconjugated diene having four to 12 carbon atoms per molecule and avinyl-substituted aromatic compound having no more than 24 carbon atomsper molecule, is sandwiched between said first and said third blocksegments both of which are homopolymer blocks of said vinyl-substitutedaromatic compound.
 3. The article of claim 2 wherein said copolymer issaid branched block copolymer.
 4. The resilient material of claim 1wherein said particulate rubber consists of tire buffings.
 5. A processfor the preparation of a resilient article comprised of a curedparticulate rubber and a binder material comprised of an uncured highgreen strength butadiene-styrene copolymer and a coumarone-indeneresinous tackifier, said process comprising contacting said particulaterubber with said binder material in a sufficient quantity of an organicsolvent to thus form a mixture, forming said mixture into aconfiguration desired of said article when complete, and permitting saidsolvent to evaporate from said formed mixture to thus produce thecompleted, dry, solid, resilient article wherein the weight ratio ofsaid particulate rubber to said binder material is in the range of 100parts by weight particulate rubber per 6 to 60 parts by weight bindermaterial wherein the weight ratio of said copolymer to said tackifier isin the range of 1:1 to 4:1, and further wherein said copolymer is one ofa branched block copolymer and a linear block copolymer wherein: saidbranched block copolymer is comprised of at least three block copolymerbranches radiating from a nucleus, each of said block copolymer brancheshaving at least two polymer block segments made from conjugated dieneswhich comprise 40 to 95 percent by weight of said branched blockcopolymer and vinyl aromatic compounds which comprise 5 to 60 percent byweight of said branched block copolymer; and wherein said linear blockcopolymer is comprised of a first block segment, a second block segment,and a third block segment wherein said second block segment, a copolymerof a conjugated diene having four to 12 carbon atoms per molecule and avinyl-substituted aromatic compound having no more than 24 carbon atomsper molecule, is sandwiched between said first and said third blocksegments both of which are homopolymer blocks of said vinyl-substitutedaromatic compound.
 6. The process of claim 5 wherein the weight ratio ofsaid solvent to said binder material is in the range of 1 to 5 parts byweight solvent per one part by weight of said binder material.
 7. Theprocess of claim 6 wherein said binder material is contained in anemulsion, said emulsion being comprised of said binder material, saidorganic solvent, water and a suitable surfactant wherein said water insaid emulsion is present in the range of 20 to 65 percent by weight ofthe total weight of said emulsion, and during said evaporation step saidwater evaporates as well as said solvent.
 8. The process of claim 7wherein said solvent is a mixture Of trichloroethylene and xylenewherein said trichloroethylene is present in said solvent mixture to theextent of about 60 percent by weight of the total weight of said solventmixture.
 9. A process according to claim 5 wherein said particulaterubber consists of tire buffings.